Bastnasite
A Review of the Mineral Processing and Extractive Metallurgy of Rare Earth Minerals
Patrick R. Taylor
The Kroll Institute for Extractive Metallurgy Colorado School of Mines
PRESENT
Geology Waste Treatment, Processing & Minimization Education Engineering Economics Energy Environment
Mining
Mining
Recycle
Physical Metallurgy
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US Potential Resources
US Potential Resources
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The rare earth metals include sixteen elements: yttrium (atomic number 39), lanthanum (57), cerium (58), praseodymium (59), neodymium (60), promethium (61), samarium (62), europium (63), gadolinium (64), terbium (65), dysprosium (66), holmium (67), erbium (68), thulium (69), ytterbium (70), and lutetium (71). The elements with atomic weights 57 to 71 are collectively called the lanthanides since they all have properties similar to lanthanum. Scandium (21) is sometimes included as a rare earth metal since it is chemically similar to yttrium and the lanthanides.
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Energy Critical Elements, American Physical Society & Materials Research Society, 2011.
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One major use of rare earth metals is as catalysts in petroleum refining. They also have many metallurgical applications as pyrophoric alloys. Another application is the use of lanthanide oxides as a constituent of high quality optical glass. The current high interest is due to rare earth applications (magnets) used in many new energy and defense applications and the Chinese control of supply.
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Uses
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Ceramics 4%
Polishing 4%
Phosphors 31%
Magnets 37%
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The two major minerals used as sources of rare earth metals are monazite (Ce-La-Nd-Pr phosphate) and bastnasite (Ce-La-Nd-Pr fluorcarbonate). Monazite is, or has been, mined in Australia, India, the United States, and other areas to a lesser degree. Bastnasite is primarily mined in the United States and China. Several other ores are mined for the rare earths as well, including xenotine, apatite, yttrofluorite, cerite, and gadolinite.
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Minerals
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Rare earth mineral ores have been mined domestically by two companies at mines locations in California (bastnasite ore) and in Florida (monazite ore). The bastnasite mining was principally for the recovery of the rare earths. The monazite mining occurred in conjunction with the processing of heavy mineral sands for titanium and zirconium recovery.
US Operations
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Covert the as-mined ore into a product that may be marketed or treated further. This involves the removal of impurity compounds from the material being processed. For Rare Earths, this is complicated by the special operations required to separate the rare earths from each other (chemically).
Mineral Processing
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In placer deposits, monazite may occur as a minor constituent along with sillimanite, garnet, and magnetite, while the major minerals are ilmenite, rutile, zircon and quartz. Other minerals that may occur in some locations are: cassiterite, chromite, picotite, baddeleyite, cinnabar, gold and platinum. Beach sand deposits may exhibit considerable variation and thus their flow sheets may be variable in detail. The next figure shows a general overview of beach sand processing.
Monazite
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Example Flow Sheet Mineral Processing Gravity, Magnetic and Electrostatic Separations
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Some resources may be treated by utilizing the differences in properties (density, magnetic susceptibility, conductivity) of the minerals.
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The ore undergoes grinding, spiraling, or other similar operations for the initial coarse upgrading of the ore. Magnetic separation removes the magnetic ore constituents which can be processed separately or discarded as waste. The refined ore is then digested with sulfuric acid at 200220oC. Rare earth sulfates and thorium sulfates are then dissolved and removed from the waste monazite solids by filtration. Rare earth elements are then precipitated as oxalates or sulfates. These precipitates undergo separations to form rare earth oxides.
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Mineral Separations
Ilmenite, garnet, xenotime and monazite, in decreasing order of magnetizability, behave as magnetic minerals. Xenotime is more strongly magnetic than monazite. In electrostatic separations, ilmenite and rutile act as conducting materials. Xenotime is a poor conductor and can be separated from ilmenite. Leucoxene can cause problems in the separation of monazite from ilmenite. A reduction roast of at 600 c converts the iron oxide in leucoxene into magnetite and enables easy separation.
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Flow sheet uses gravity, magnetic and electrostatic separation at different separation factors
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The resulting slurry is filtered and the solution is treated with sodium hydroxide to produce rare earth hydroxides. This rare earth hydroxide cake is chlorinated, converting the hydroxides to chlorides. Final filtration and evaporation yields the solid rare earth chloride products.
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30-35% solids. Rougher flotation brings the grade from about 9% to 20% REO. Tails are 1-2% REO. Four stage cleaning is used tailings are re circulated. The scavenger cons are reground and recirculated to roughers. After four stage cleaning, the final concentrate is thickened, filtered and dried The grade is 60% REO and the recovery is 65-70%
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A very complex flow sheet that requires significant energy and chemicals. Research may lead to alternative surface chemistry and flotation processes.
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Numerous minerals occur intimately intergrown in the rare earth Bayan Obo iron ore. In addition to REO, products include: magnetite, hematite, fluorite and niobium oxide. Bulk flotation is carried out on 90% < 74 micron material with sodium carbonate to adjust pH, sodium silicate to depress iron and silicate minerals and a sodium salt of oxidized petroleum (paraffin soap) as collector. The flotation tailings are taken to iron and niobium recovery circuits.
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The cons are retreated after eliminating excess fatty acids and de sliming using sodium carbonate (pH 5-6), sodium silicate and sodium fluosilicate (depressants) and hydroxamic acid (collector). Rougher cons are 45% REO and has both monazite and bastnasite. Recovery is about 80%. Final treatment by cleaning or high intensity magnetic separation gives two fractions a primary 68%REO concentrate and a secondary monazite concentrate (36% REO), with respective recoveries of 25% and 36% - 61% total.
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Once a concentrate is obtained, then the metals of interest must be extracted from the material. Several approaches are possible, usually involving calcining and acid leaching. The solutions are then subjected to ion exchange or solvent extraction for purification.
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The sulfuric acid method has been used extensively in the US. Thorium and rare earths may be selectively, or totally, extracted depending on the conditions. The processes available are shown in the following figure. Rare earth recovery is based on double sulfate precipitation. Yttrium and the heavy rare earths are very soluble and go along with thorium.
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Separations Processing
Using fractional crystallization, one or more rare earths in a mixture are precipitated by changing the salt concentrations in solution through evaporation or temperature control. Fractional precipitation involves adding a precipitating agent to selectively remove a metal from solution. A vide variety of processes have been developed to recover specific rare earths by these two techniques.
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Solvent Extraction
Liquid-liquid solvent extractions are often performed to separate a mixture of rare earths from each other, i.e., tributyl phosphate, which selectively extracts one rare earth from the others. Several stages of extractions are needed to separate each rare earth metal. Example extractants are shown in the next slide.
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Ion Exchange
Ion exchange may be used to produce highly pure rare earths. Since the rare earths form trivalent cations (3+), a cation exchange resin might be used. For separating a mixture of lanthanides, the resin is first flushed with a solution such as cupric sulfate to prepare the resin for ion Exchange. A solution containing the lanthanides is then passed over the ion exchange resin. The lanthanides displace the cation, in this case cupric, on the resin surface.
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Ion Exchange
To separate individual rare earth elements, an element containing a complexing agent, such as ammonium ethylenediamine tetra acetic acid (NH4+EDTA), is passed over the resin. The EDTA has a high affinity for rare earths, and the lanthanides are complexed with the EDTA and displaced by NH4+ on the resin. Each lanthanide has a different affinity for EDTA, and individual lanthanides can be separated and recovered as a result of these varying affinities.
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Metal Production
High purity rare earth metals can be produced by the metallothermic reduction of rare earth halides. This process is used when high purity is required. After converting the rare earths into fluorides, they are reduced to the metallic state through contact with calcium or barium at high temperatures. Fused salt electrolysis is also used.
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Introduction to Reduction
Rare earth oxides are the end products of mineral processing, leaching and separations. These oxides are extremely stable and their reduction is difficult. This is compounded by the metals melting points and vapor pressures. Conversion of the rare earth oxide to a halide and reduction of the halide is a useful approach. Fused salt electrolysis is also a useful approach. This would be most useful for the lower melting point rare earth metals. The preparation of a rare metal by forming an alloy and then recovered from the alloy is another potentially useful approach.
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Introduction to Reduction
Every process has certain advantages and limitations with respect to applicability to individual rare earths, purity of product, yield of the metal, batch size, operational convenience, economy and environment. In spite of their chemical similarity to their trivalent states, the rare earths do display considerable variation in properties like melting point and vapor pressure. Another factor is the possibility of di-valency in some rare earth elements. This frustrates attempts to produce them by the usual chemical and electrolytic reduction processes.
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Introduction to Reduction
Under nonstandard conditions, that are more typical of real processes, pure components are not typical, so the activities play a significant role in the reaction potential. Activities less than unity changes the Gibbs energy of the reaction and can lead to more favorable conditions. Methods would include: the formation of a metal with a low boiling point and hence vaporizing in a metallothermic reaction, recovery of the reduced metal as an alloy, and trapping the compound formed by the reduction in a complex slag. Also, carbothermic reduction under vacuum may be an efficient reduction at high temperatures.
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Metallothermy
The metallothermic reduction reaction may be represented by the equation: M(I)Xn + iM(II) = M(I) + iM(II)Xn/I Where M(I) is the metal to be produced, X is the anion, and i,n are the stoichiometric coefficients. Feasibility is determined by thermodynamics. Practicality is determined by melting point, boiling point, vapor pressure, density, viscosity (for liquid components), and characteristics such as chemical reactivity, and alloying behavior of the reactants and products.
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Metallothermy
These reactions are generally exothermic, and by suitable choice of reactants, materials and process conditions it has been possible to realize many of the characteristics listed. The reactants in a powder form favors better contact and once initiated a quicker reaction. If the heat generated during the reaction is sufficient to raise the temperature of both slag and metal above their melting points, and if they remain molten for a sufficient length of time, so that the denser metal settles by gravity with the immiscible (slag) layer on top, a metal ingot and solidified slag may be obtained. When the heat of reaction is insufficient, other types of products can form.
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Metallothermy
If the reaction occurs but the slag does not melt, the metal is formed as a powder in the slag. The slag is then leached away to obtain a metal powder. Metal in the form of powder can also form when the slag melts, if the melting point of the metal is very high and the metal is not sintered; but may form a coalesced sponge. Metal is recovered by slag leaching or vacuum distillation. By suitable choice of reductants, reactors and reaction conditions, the metal can usually be obtained in the chosen form. Rare Earth metals have been obtained by metallothermic reduction in the form of ingot, sponge or powder.
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Metallothermy
Metal ingot has been obtained using metallothermic reduction of rare earth fluorides as well as some of the chlorides using calcium as a reductant. Sponge of some rare earth metals have been produced from chlorides using lithium as the reductant. Rare metal powders have been obtained by reducing oxides with calcium. Certain rare earth alloys can be directly produced in ingot, sponge or powder form, followed by vacuum distillation. Purity depends on the purity of the starting materials, pure oxides, anhydrous chlorides or fluorides, reductants and reaction steps
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These methods to reduce REOs is complicated by the stability of these oxides. This requires significant purification prior to reduction or very complex refining schemes. Research on new reduction and refining methods may lead to alternatives.
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Chloride Reduction
Calcium, in a dolomite lined steel bomb, has been used to reduce cerium trichloride. Additional heat was provided by using calcium iodide booster reaction. After completion, the slag was removed and the metal vacuum melted to remove any excess calcium or calcium chloride slag. Purity was 98% and yield was 95%. Also used for lanthanum, praseodymium and neodymium.
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Reduction-Distillation - Lanthanothermy
Similar to the Pidgeon Process for Mg can be used for samarium, europium and ytterbium (not obtained through halide routes). Vapor pressure measurements of the rare earth metals have indicated that lanthanum was the least volatile of the rare earths and that dysprosium had a vapor pressure nearly 300 times higher. Samarium and europium are also very volatile. Lanthanum oxide has one of the highest (-) heats of formation among the rare earth oxides. This led to a process for reducing these oxides with lanthanum and volatizing the products.
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Lanthanothermy
Samarium and Ytterbium were prepared by heating the oxides with La in tantalum crucible at 1450 C and 0.1 Pa for one half hour. Europium was prepared by reaction with La in the reactor shown. Heated to 1000 C at 0.02 Pa and then to 1100 and 1200 C. Samarium, if present, is not volatile.
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1.5
1.0
Tm2O3
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0.0
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Temperature 2000 C
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Electrolysis Introduction
Unlike the chemical reduction processes, electrolytic reduction does not rely on the availability of reducing agents and limited by the relative chemical stability. The Gibbs energy is related to the decomposition potential by: Go = nFEo It can be shown that an applied potential as small as 4 V should be adequate to dissociate even the most stable of compounds. This is only one of several requirements for effective methods to reduce stable rare earth compounds to metals. The process for electrolytic reduction of salts or compounds is basically simple.
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Electrolysis Introduction
The salt of a metal is dissolved in another salt or mixture of salts that are kept molten in an inert container. Two electrodes a cathode and an anode are inserted into the molten bath and an electric current is passed through the circuit, with a voltage sufficient to reduce the salt. The molten salts (carrier electrolyte) serves as a solvent for the metallic salt to be reduced (functional electrolyte).
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Electrolysis Introduction
The carrier electrolyte is chosen to have a desirable solubility of the functional electrolyte, sufficient conductivity for the electric current, a melting point below the desired operating temperature of the cell, low vapor pressure, and a greater stability than the functional electrolyte. These properties are normally obtained using an alkali or alkaline earth fluoride or chloride or a mixture of both. Considerable variability in cells used is seen: size, shape, materials of construction and disposition of the electrodes.
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Electrolysis Introduction
Iron, Graphite, ceramics such as fire brick and alumina, refractory metals such as molybdenum and tungsten have all been used as cell materials. The anode is usually made of graphite and the cathode is iron, molybdenum or tungsten. Often the cell itself is the anode or cathode. Heat is supplied in two ways: the electrical current to the cell is used to supply the necessary heat or an external furnace is used.
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Electrolysis Introduction
The largest amount of commercial rare earth metals are produced by electrolytic methods. La, Ce, Pr and Nd have melting points that permit recovery in the liquid state by electrolysis of relatively inexpensive chlorides at temperatures less than 1100 C. This facilitates metal slag separation, minimizes contamination of the metal, and enables continuous operation and high volume levels of production. The technical feasibility of producing high melting point rare earth metals (Gd, Dy and Y) has been demonstrated by using fluorides in place of chlorides in specially designed high temperature cells.
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Electrolysis Introduction
The advantage of liquid metal recovery and low temperature operation have been realized even in the case of high melting point Rare Earth metals by using metals like: Cd, Mg, Zn, Mn, Cr and Co as cathode. These metals form liquid alloys with the rare earth metals as it electrodeposits and liquid product recovery is facilitated.
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Chloride Electrolysis
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Oxide-Fluoride Electrolysis
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Recovery as Alloys
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Refining is complex as well and may involve vacuum melting, vacuum distillation, zone refining etc.
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What are the thrusts and requirements for a research program in this area? Re-evaluate the current state of the technology available for rare earth resource processing. Identify and do research on those aspects that could be improved utilizing new mineral processing, extractive metallurgy and metal refining technology. Address the ultimate disposition of problematic elements in the solid and aqueous discharge. Help developed a trained engineering work force to tackle the research, development and production aspects. Finally, keep in mind that economics is always the bottom line in any resource recovery operation.
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Extractive Metallurgy
Much of the current utilized extractive metallurgy technology for rare earth elements was developed many years ago and there have been several significant advancements in our understanding of chemical processing methods for extraction and separation. Among these advancements have been: Excellent chemical thermodynamics screening methods using Gibbs energy minimization. Improved extraction methods based on increased understanding of chemical kinetics, reactor design and transport phenomena (heat, mass and momentum). Improved understanding of solution purification techniques, such as solvent extraction and ion exchange. Improved models and software for chemical reactor and flow sheet design.
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Edgar E. Vidal Research Associate Professor of Metallurgical and Materials Engineering EXPERTISE Extractive and process metallurgy Pyrometallurgy Recycling Waste treatment and minimization.
D. Erik Spiller Research Professor of Metallurgical and Materials Engineering EXPERTISE Mineral Processing Leaching Project management: feasibility, engineering, construction management, operations
Gerard P. Martins Professor of Metallurgical and Materials Engineering EXPERTISE Process and extraction metallurgy Electrochemical systems Transport phenomena Reactor Design & kinetics
Paul B. Queneau Adjunct Professor of Metallurgical and Materials Engineering EXPERTISE Extractive and process metallurgy Pyrometallurgy Recycling Waste treatment and minimization.
Judith C. Gomez Research Assistant Professor of Metallurgical and Materials Engineering EXPERTISE Extractive and process metallurgy Materials synthesis Recycling Waste treatment and minimization
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What KIEM can do for the mining and rare earth industry
Offer senior/graduate level (full or short) courses in mineral processing-extractive metallurgyrecyclingwaste minimization in the evening, by web or video, or on-site. Develop engineering talent for future employment. Encourage and market opportunities in industry to our undergraduate and graduate students. Perform research in support of industry goals. Maintain at least one significant program in the US with an emphasis on mineral processing-extractive metallurgy.
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Primary References
Extractive Metallurgy of Rare Earths, C.K. Gupta and N. Krishnamurthy, CRC Press, 2006 Various technical publications and patents
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Hill Hall, home of KIEM Please come see what were up to. THANK YOU.
The Kroll Institute for Extractive Metallurgy George S. Ansell Department of Metallurgical and Materials Engineering Colorado School of Mines www.mines.edu
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